Copper containing disazo dyestuffs of the stilbene series



United States Patent COPPER CONTAINING DISAZO DYESTUFFS. THE STILBENE SERIES Y Ernst Keller, Binningen, Basel lland, and Rudolf Durig, Basel, Switzerland, and Fritz Mindermann, Grenzach, Baden, Germany, assignors to J. R.- Geigy A.-G., Basel, Switzerland, a Swiss firm g No Drawing. Application December 4, 1956 Serial No. 626,084 Claims priority, application Switzerland December 16, 1955 I Claims." (Cl. 260-146) The invention concerns substantive'disazo dyestutls of the stilbene Series, their production and their use for the dyeing of cellulose or of material containing cellulose fast to light green to' o live green shades. It also concerns', as industrial product, the material dyed with'the aid of these dyestuffs.

2,882,266 Patented Apr. 1959 2 g N-acyl derivatives of 2-amino-G-hydroxynaphthalene- 8-sulphonic acid can be used as azo components to be coupled with thediazo compound of the amino monoazo dyestufl? of the general Formula I, the acyl radical of which canbe derived from organic sulphonic acids and, advantageously from organic carboxylic acids dr-den'vatives of carbonic acid. The preferred N-acylamino compounds can contain radicals of aliphatic or aromatic car- 0 acid for example can be used.

It has been found that valuablesubstantive disazo dyestufis are obtained when an aminomonoazo dye'stufi of the general Formula I K wherein A represents the radical of a 4-f[4.5-naphtho- 1.2 .3-triazolyl-(2)l-stilbcne-2.2'-disulphonics acid. bound The. disazo dyestufis of the stilbene series producedin this manner are coppered by methods known per se,-a dvantageously in aqueous solution or suspension at a raised temperature, by treatment with agents giving oil-copper.

A'modification of the order in which the dyestuifs according to the present invention are built up consists in T diazotising an amino monoazo dyestulf of the general to the a zo group in the 4'-position, and R represents-a low molecular alkyl group which may possibly be substitutedjis diazotised, coupled with a 2-acylamino-6-hy:

droxynaphthalene-8-sulphonic acid and the disazo dyestufi 1 so obtained is converted by treatment with agents giving ofi copper into the corresponding complex? copper compound. I

The amino monoazo dyestufis'of the general Formula I used in the process according to the present invention are obtained by coupling diazotised 4-amino-4-[4.5-naphtho 1.2.3-triazolyl-(2)1-stilbene-2-.2 -disulphonic acids with l-amino-Z-alkoxynaphthalene monosulphonic acids. Ad-.-

v Formula II OzH (II) wherein R has the meaning given above, then coupling the diazo compound with a 2-acylamino-G-hydroxynaphthalene-S-sulphonic acid, reducing the nitro group to the amino group and then coupling the amino disazo dyestufl obtained, after diazotisation, with an azo component coupling in the o-position to a primary amino group.

vantageous examples of the latter are l-amino-Z-alkoxynaphthalene-6-sulphonic acids having low molecular substituted or unsubstituted alkyl groups, e.g. the methyl, ethyl, or carboxy methyl radical.

The -amino-4-[4.5-naphtho-1.2.3-triaao1yl-(2)l-stilbene-2.2'-disulphonic acids used as starting materials in the production of the amino monoazo dyestufis of the general Formula I are known, or they can be produced by methods known per se. 'aminostilbene-2.2-disulphonic acid is coupled with an azo component coupling in the o-position to a primary amino group, the o-amino monoazo dyestuif formed is oxidised For example, diazotised 4-nitro-4'- "In this formula: Ar represents a naphthalene radical The triazole ring is then closed and the copper complex formed, it being posisble to perform both these reactions in one step, e.g. by treatment with ammoniacal copper sulphate solution.

In their non-copper containing form, the disazo dyestutfs whichare produced according to the present invention correspond to the general Formula III .1:

OiH

zen- B (III) which is bound to the nitrogen atoms by two C atoms next to each other in the nucleus, B represents an acyl radical and preferably the substituent COD, wherein D is a possibly further substituted alkyl, alkoxy or aryl group, and R represents a low molecular alkyl radical which may possibly be substituted. y

In the form of their alkali'salts, e.g. the lithium, sodi to form the l.2.3-triazole compound and the nitro group 5 "um, potassiumor ammonium salts, the cupriferous disazo is reduced to the amino group.

Aminonaphthalene compounds such as e.g. Z-aminonaphthalene, Z-aminonaphthalerie-L, -5-, -6-, -7-, or -8-,,

'monosulphonic acid, l-aminonaphthalene-S- or -4-sulphonic acid, 2-aminonaphthalene-3.6- or -5.7- or -6.8-disulphonic acid can be used as azo components coupling in the'o-position to a primary amino group.

dyestufis according to the present invention are dark coloured, Water soluble-powders. They dye cellulose or material containing cellulose from a bath containing Example 1 I I niiirqcndmgrhn it N soar mm 0.2: 03H I s in.

132 parts of 4-nitro-4'-aminostilbene-2.2'-disulphonic 2-benzoylamino-6-hydroxynapl1thalene-8-su1phonic phonic acid. This aminoazo dyestuif is further diazotised and the diazo compound is coupled with 51.4 parts o;

aci

NHGO

in the presence of pyridine; The disazo dyestulf so obacid are diazotised in the usual way and coupled in an 5 tained is isolated. To convert it into the complex copper acetic acid solution with 76 parts of 2-aminonaphthalenecompound, it is dissolved in water and boiled for 12 hours 6sulphonic acid. The monoazo dyestulf formed is pre-- in the PfeSeIlCe 0f sqdlum acetate Wlth P of copper cipitated with sodium chloride, isolated and again dis- P After drym?! complefely copperfid dyesmfi solved in water. It is then converted by treatment with 18 a dark Powder ,whlch dlssolves water wlth blue 410 parts of 12% sodium hypochlorite solution in the 20 green and thaws l g f presence of 26.5 parts of sodium carbonate at a tern cellulose: fibres fromanvaqueous bath m.fun greens a a The dyemgs have very good fastness to light and the shade; perature of -60 into the tnazole compound. The and f m to ht at 0111 vs slight! affected by triazole compound is precipitated with sodium chloride, gj f e y W y I and s z i 1s.reduced usual way 5 Further dyestufis are given in the table below which Aron an 2 P the ammo are obtained in a similar manner, i.e. by diazotising the. Parts of 4 [6 'sulPhonaPhthml amino azo dyestuffs obtained from columns 1 and 2 and tnazolyl-(2 )]-stilbene-2.2'-d1sulphomc acid so obtained mupling with the and components shown i lu n 3 are diazotised and coupled in a soda alkaline solution a d finally converting the free forms into the correspondwith 38 parts of 1-amino-2-methoxynaphthalene-6-sulg. ing copper complexes.

No. Starting component Middle component End component Shade BOaH 0cm 0:: 1.. WHON- Nn, son! Green.

OH NH: SOH

OH 01H NHO'OCH:

801E OCH; 0H

2. nan N-N NH, v sou; no.

OH NH;

: 0:11 OlE NHOOOE:

SO'H OsH NHOQOOHI' SOzH OH 5-......-.... KEG-N ki som Do.

OH NH:

cm on; nnooomso-a v Exa pie 2 a i her selected from the group. consisting of lower alkyls.2..parts of the dyestuif obtained according toExample ,5 carbonyl lower fl 9 alkylsulhnyl and are dissolved in a dyebath fggoo n f. phenylcarbonylt radicals, and n 15 one of the numerals water and 1 part of soda. 100 parts of cotton are en- 1 and a. i

tered at 40-50", the bath is heated to 90-95 within 30 5 2- "Ih compl x pp compound of a disazo dyeswfi minutes, 30 parts of sodium sulphate are added and dye- ,having the formula;

. j N-N-Q-tiikdEQ-NQQ r x 0.1: I out ing is continued for 45 minutes at this temperature. 3. The;complexfcopper compound of a disazo dyestufi this time, the dyed goods are rinsed cold in the usual having the formula: I

. oom on ki -N831: @803 I 2 0,3 OOOHs way and dried. In this manner the co n is dyed in 4.' The complex copper compound of a disazo dyestufi green shades which have good wet fastuess andyery having theformula:

. II 0cm OH is): I corn *5 I 0a 1 8 light imam p p 1 t 5; 'Ihe'oomplex copper compound of a disazo dyestufi What we claim is: having the formula:

' v I com on v N TQOH OEQN=N N-N 50m l N on I 0-H I II 3 i i I t om :moooom out r f I 1. The complex-copper. compound of agdisszo dyestufl I having; the general formula: I-

I N om on: (noisy.- I i I i 1 F Q wherein R represents a member selected from the group References Cited in the tile of this patent consisting Of CH; and -CH3C0OH, B represents ,3 mem- UNITED STATES PATENTS 2,115.55; Schindhelm m1. 

1. THE COMPLEX COPPER, COMPOUND OF A DISAZO DYESTUFF HAVING THE GENERAL FORMULA: 